US10544277B2 - Process for making gray expanded polystyrene - Google Patents
Process for making gray expanded polystyrene Download PDFInfo
- Publication number
- US10544277B2 US10544277B2 US15/787,083 US201715787083A US10544277B2 US 10544277 B2 US10544277 B2 US 10544277B2 US 201715787083 A US201715787083 A US 201715787083A US 10544277 B2 US10544277 B2 US 10544277B2
- Authority
- US
- United States
- Prior art keywords
- styrene monomer
- additive
- amount
- radical initiator
- free radical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active, expires
Links
- 239000004794 expanded polystyrene Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims description 67
- 230000008569 process Effects 0.000 title description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 95
- 239000011324 bead Substances 0.000 claims abstract description 55
- 239000006229 carbon black Substances 0.000 claims abstract description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 47
- 239000010439 graphite Substances 0.000 claims abstract description 47
- 239000004793 Polystyrene Substances 0.000 claims abstract description 34
- 239000000654 additive Substances 0.000 claims abstract description 34
- 229920002223 polystyrene Polymers 0.000 claims abstract description 34
- 230000000996 additive effect Effects 0.000 claims abstract description 30
- 238000010557 suspension polymerization reaction Methods 0.000 claims abstract description 24
- 238000009826 distribution Methods 0.000 claims abstract description 22
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 21
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 17
- 239000003999 initiator Substances 0.000 claims description 63
- 150000003254 radicals Chemical class 0.000 claims description 50
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000002270 dispersing agent Substances 0.000 description 13
- 239000004094 surface-active agent Substances 0.000 description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 10
- 238000007792 addition Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000001506 calcium phosphate Substances 0.000 description 8
- 238000009472 formulation Methods 0.000 description 8
- 230000003993 interaction Effects 0.000 description 8
- -1 polyethylene Polymers 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical group [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 8
- 229940078499 tricalcium phosphate Drugs 0.000 description 8
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 8
- 235000019731 tricalcium phosphate Nutrition 0.000 description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 description 7
- 238000009413 insulation Methods 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000004604 Blowing Agent Substances 0.000 description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009435 building construction Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical group [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229920006248 expandable polystyrene Polymers 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/06—Hydrocarbons
- C08F12/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/16—Making expandable particles
- C08J9/20—Making expandable particles by suspension polymerisation in the presence of the blowing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
- C09C1/48—Carbon black
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/01—High molecular weight, e.g. >800,000 Da.
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/04—Broad molecular weight distribution, i.e. Mw/Mn > 6
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/06—Polystyrene
Definitions
- the present invention relates to methods for preparing expanded polystyrene (EPS), and more particularly relates, in one non-limiting embodiment, to methods for preparing gray EPS with a desired bead distribution by suspension polymerization.
- EPS expanded polystyrene
- EPS Expandable Polystyrene
- EPS Expandable Polystyrene
- Multiple formulation systems have been used depending on the equipment available, polymerization process used, and desired end use properties.
- EPS can be made using multiple techniques, including extrusion of polystyrene with addition of blowing agents through underwater dies to form expandable beads or suspension polymerization of styrene monomer with subsequent addition of blowing agents.
- EPS Insulation grade EPS
- Normal “white” grade EPS provides efficient, light weight insulation, and is widely used for home and commercial building construction.
- Improved insulation values have been obtained by adding graphite or carbon black to insulation grade EPS to give gray EPS. These grades provide improved insulation performance (measured as thermal conductivity, or lambda) vs. the normal “white” grades when formed at the same mass, or can provide equal insulation when formed with less mass.
- the carbon black and/or graphite must be dispersed efficiently within the EPS. This can be accomplished through the use of mechanical shear, dispersing agents, or a combination of dispersing agents with mechanical shear. Additionally, processes for production of carbon black and/or graphite can be modified to change the surface characteristics of the carbon black and/or graphite particles, and improve the ability to disperse these particles within polymers such as EPS.
- the efficient mixing of carbon black and/or graphite in EPS can be made easier through the use of carbon black and/or graphite masterbatches, where relatively high concentrations of carbon black and/or graphite have been mixed with polystyrene under high shear conditions and then extruded to form pellets.
- the use of dispersing agents may also be used in combination with the high shear conditions to make masterbatches.
- the masterbatches also have the advantage of creating less dust while handling carbon black and/or graphite.
- the addition of carbon black and/or graphite is known to improve the insulation values of EPS beads.
- the addition of carbon black and/or graphite is established art.
- producing gray EPS using the suspension polymerization method is more challenging.
- the addition of carbon black and/or graphite to the suspension formulation can create emulsion instability, leading to poor bead size distribution or even invert the emulsion from styrene in water to water in styrene, which can lead to gelling of the reactor.
- Previous art teaches that the suspension method may be used, but notes the addition of about 3-20% polystyrene to the styrene monomer improves the stability. It has been found that achieving desired bead distributions and cell structure can be difficult even using these levels or even higher amounts of polystyrene.
- the carbon black and/or graphite can interact with the radical initiators, requiring much higher levels of the radical initiators to achieve the targeted amount of polymerization.
- the interactions between radical initiators and carbon black and/or graphite can also create a variation in the polymerization rate.
- EPS formulations already employ polyethylene wax as a processing agent to improve the cell structure of the EPS bead.
- Polyethylene waxes can also provide improvement for dispersion of carbon black or graphite within the EPS bead, as disclosed in W. P. Cottom, “Additives for Expanded Polystyrene Suspension Formulations”, IP.com, IPCOM000244928D, 1 Feb. 2016), as well as minimize the interaction between the carbon black and/or graphite and the radical initiator.
- Other products disclosed included alcohols, ethoxylates, carboxylic acids, polymers, copolymers, oxidized polyethylenes, and modified waxes.
- a method for preparing gray expanded polystyrene includes polymerizing styrene monomer to polystyrene by suspension polymerization; then, only after approximately 20 to 60 wt % of the styrene monomer has been converted to polystyrene, introducing to the suspension polymerization an additive selected from the group consisting of carbon black, graphite, and combinations thereof; and after a period of polymerizing to ensure good mixing and allow droplet size to equilibrate to a desired range; in one non-limiting embodiment of about 0.1 mm to about 1.0 mm; then continuing to polymerize the styrene monomer to polystyrene by suspension polymerization to produce gray EPS.
- EPS gray expanded polystyrene
- expanded styrene polymers are styrene polymers containing blowing agents.
- the blowing agents may be conventional.
- the target parameters of the gray EPS produced by the method described herein will vary depending on the item to be made and its ultimate end use.
- the gray EPS has a weight average molecular weight between about 50,000 independently to about 1,000,000 amu; alternatively from about 150,000 to about 750,000 amu.
- the term “independently” means that any threshold may be used together with another threshold to give a suitable alternative range.
- a suitable molecular weight range may be from 50,000 to about 150,000 amu.
- a precise or actual mw is not that relevant since customers choose different molecular weights to accomplish different purposes in different applications.
- the method described herein permits reproducibly forming the beads of any target molecular weight size.
- the gray EPS has a bead size between about 50 independently to about 1500 microns; in one non-limiting embodiment between about 500 independently to about 1300 microns; alternatively between about 850 independently to about 1170 microns. Nevertheless other ranges may be used for making different parts.
- suitable bead distribution is from about 10 independently to about 90 weight % of the beads in the range of about 850 independently to about 1170 microns; alternatively from about 35 independently to about 90 weight % of the beads in the range of about 850 independently to about 1170 microns.
- the desired cell structure generally means that the cell structure is uniform so that the expansion will be uniform.
- a preferred range for cell size will vary depending on the part to be made. It can be important to be able to adjust the method to hit the desired target. In one non-limiting embodiment, the cell size ranges between about 4 independently to about 20 cells per millimeter; alternatively the cell size ranges between about 8 independently to about 16 cells per millimeter.
- the polystyrene density may range from about 5 independently to about 35 g/l (grams/liter), alternatively from about 8 independently to about 25 g/l, and in another non-limiting embodiment from about 10 independently to about 15 g/l.
- the dissolving rate is controlled by the molecular weight of the polystyrene used in the masterbatch, the size of the masterbatch pellets, the amount of remaining styrene monomer, the reaction temperature, and the stirring rate.
- This process allows the carbon black and/or graphite to also be evenly dispersed into the monomer droplets, but minimizes the interactions between the carbon black and/or graphite and radical initiator, surfactant, and dispersing agent until at least 20-60 wt % of the styrene has been converted. After the majority of the polystyrene has been solvated by the styrene monomer, the interaction between the carbon black and/or graphite and radical initiator dramatically slows down the polymerization rate.
- This slower polymerization rate allows time for the droplet size to equilibrate to the desired range and for the carbon black to mix efficiently.
- This desired droplet size range is between about 0.1 mm and about 1.0 mm.
- An additional dose of radical initiator can then be added to complete the polymerization.
- the additional dose of radical initiator is far less than the amount needed if the carbon black and/or graphite is added at the beginning of the reaction.
- the desired droplet size ranges from about 100 independently to about 1000 microns; alternatively from about 75 independently to about 1500 microns; and in another non-restrictive version from about 50 independently to about 2000 microns.
- any molecular weight masterbatch may be used, in any size pellets. What may be important is that it will take longer to dissolve with higher molecular weights and bigger pellets.
- the amount of remaining styrene monomer at the time of introduction of the predispersed masterbatch ranges from about 70 independently to about 20 wt %, alternatively from about 60 independently to about 40 wt %.
- the reaction temperature may range from about 80 independently to about 100° C. followed by about 110 independently to about 140° C.; alternatively the reaction temperature may range from about 85 independently to about 95° C. followed by about 125 independently to about 135° C.
- Stirring rates depend on reactor conditions and are not necessarily a limiting factor for the methods described herein. What is important is good mixing. For the experiments described below, a suitable range is from about 200 independently to about 600 rpm; alternatively from about 300 independently to about 450 rpm.
- a primary free radical initiator may be is activated at about 90° C. in an amount from about 0.3 wt % independently to about 0.5 wt % based on the styrene monomer present, and a secondary free radical initiator is activated at about 130° C. in an amount from about 0.1 wt % to about 0.3 wt % based on the styrene monomer.
- a primary free radical initiator may be activated at about 90° C. in an amount from about 0.35 wt % independently to about 0.45 wt % based on the styrene monomer, and a secondary free radical initiator is activated at about 130° C. in an amount from about 0.15 wt % to about 0.25 wt % based on the styrene monomer.
- a second embodiment to control the addition of carbon black and/or graphite is to add fluff or powder grades to the white formulation after at least about 20 to about 60 wt % of the styrene has been converted.
- the interaction between the carbon black and radical initiator dramatically slows down the polymerization rate. This slow rate is held for an optimized period of time to allow for the droplet size to equilibrate to the desired range. Again, this optimized period of time depends on many factors including the target parameters for the gray EPS and thus even a general time period or range is difficult to specify. The optimized time period will also depend upon the size of the reactor. An additional dose of radical initiator can then be added to complete the polymerization.
- a free radical initiator may be introduced in an initial dose and in an additional or subsequent dose, for instance an initial dose in an amount from about 0.3 wt % independently to about 0.5 wt % based on the styrene monomer present and a free radical initiator is introduced in an additional dose in an amount from about 0.4 wt % independently to about 0.6 wt % based on the styrene monomer.
- a free radical initiator may be activated in an initial dose in an amount from about 0.35 wt % independently to about 0.45 wt % based on the styrene monomer, and a free radical initiator is introduced in an additional dose in an amount from about 0.45 wt % independently to about 0.55 wt % based on styrene.
- the initiator for the initial and additional doses may be the same or different.
- the additional dose is introduced after the droplet size has equilibrated within the desired size range.
- the proportion of fluff or powder grade ranges from about 5 wt % independently to about 10 wt % based on the styrene monomer; alternatively ranges from about 6 wt % independently to about 8 wt % based on the styrene monomer.
- the slowing down of the polymerization rate will vary depending upon reaction conditions.
- the standard (existing art) reaction will proceed to only about 5 wt % to 25 wt % styrene monomer remaining after three hours polymerization.
- a third non-restrictive embodiment of the method herein is to combine the predispersed masterbatch and the fluff/powder grade procedures.
- the fluff or powder grade may be added after at least about 20 to about 60 wt % of the styrene has been added, while the masterbatch can be added earlier or at the same time. If added at the same time, more time should be allowed for the polystyrene in the masterbatch to dissolve in the remaining styrene monomer before adding the additional dose of radical initiator.
- the amount of masterbatch pellets may range from about 10 wt % independently to about 22.5 wt % based on the styrene monomer, alternatively from about 15 independently to about 20 wt % based on the styrene monomer.
- the amount of fluff and/or powder grade carbon black and/or graphite may range from about 0.1 wt % independently to about 1 wt % based on the styrene monomer, alternatively from about 0.2 wt % independently to about 0.4 wt % based on the styrene monomer.
- an initial and an additional or subsequent dose may be used where the initial dose may range from about 0.3 wt % independently to about 0.5 wt % based on the styrene monomer; alternatively from about 3.5 wt % independently to about 0.45 wt % based on the styrene monomer.
- the additional dose may range from about 0.3 wt % independently to about 0.5 wt % based on the styrene monomer; alternatively from about 0.35 wt % independently to about 0.45 wt % based on the styrene monomer.
- the amount of remaining styrene monomer after three hours may be from about 70 independently to about 20 wt %; alternatively from about 60 independently to about 40 wt %.
- the proportions of carbon black and/or graphite based on the resulting styrene polymer range from about 0.1 independently to about 10 wt %; alternatively from about 3 independently to about 8 wt %.
- the graphite used suitably has an average particle size of from about 1 independently to about 50 ⁇ m; alternatively from about 2.5 independently to about 12 ⁇ m.
- the graphite may also have a bulk density of from about 100 to about 500 g/l and a specific surface area of from about 5 to about 20 m 2 /g, in a non-limiting embodiment. Natural graphite or synthetic graphite may be used.
- surfactants and dispersing agents may be used.
- a particular, non-limiting suitable surfactant is sodium dodecyl benzene sulfonate.
- a particular, suitable non-limiting dispersing agent is tricalcium phosphate.
- the amounts or proportions of surfactant or dispersing agent are adjusted to produce the desired bead size. To get the desired bead size and bead size distribution, it may be necessary to add additional surfactant and/or dispersing agent when adding the carbon black and/or graphite to the formulation. Under the process described herein, there is time for the additional surfactant and/or dispersing agent to create the desired bead size and bead size distribution before the polymer's viscosity is too high for the bead size to equilibrate.
- dibenzoyl peroxide may be used as a primary or initial initiator which functions at a temperature of about 90° C.
- t-butylperoxy benzoate may be used as a secondary or additional initiator which functions at a temperature of about 130° C.
- gray EPS with molecular weight, bead size, bead size distribution, and cell nucleation similar to those of white EPS on a consistent basis. Further, it is possible to make small adjustments to the radical initiator, surfactant, and dispersing aid to make optimized final product. It has also been discovered that the use of products such as polyethylene and long chain alcohols work very effectively in the improved process to provide better cell structure and help control bead size and distribution.
- the styrene polymers described herein can contain the customary and known auxiliaries and additives, for example flame retardants, nucleating agents, UV stabilizers, chain transferrers, chain extenders, blowing agents, plasticizers, pigments and anti-oxidants.
- auxiliaries and additives for example flame retardants, nucleating agents, UV stabilizers, chain transferrers, chain extenders, blowing agents, plasticizers, pigments and anti-oxidants.
- comonomers compatible with styrene to be copolymerized therewith may also be included; suitable ethylenically unsaturated comonomers include, but are not necessarily limited to, alkylstyrenes, divinylbenzene, acrylonitrile, ⁇ -methylstyrene and combinations thereof.
- the polystyrene beads were washed with water and dried. The beads were then classified by size in a Gilson shaker using #10 (2000 microns), 14 (1400 microns), 16 (1180 microns), 20 (855 microns), 25 (710 microns), 30 (600 microns), 35 (500 microns), and 45 (355 microns) sieves.
- Example 1 was repeated two weeks later using the same equipment, same reagents, and same conditions.
- Example 3 was repeated 10 weeks later using the same equipment. The same reagents were used except for a new batch of PS6310. The results of Examples 1-4 are summarized in Table I.
- the present invention may suitably comprise, consist of or consist essentially of the elements disclosed and may be practiced in the absence of an element not disclosed.
- EPS gray expanded polystyrene
- the method consists essentially of or consists of polymerizing styrene monomer to polystyrene by suspension polymerization; only after approximately 20 to 60 wt % of the styrene monomer has been converted to polystyrene, introducing to the suspension polymerization an additive selected from the group consisting of carbon black, graphite, and combinations thereof; and after a period polymerizing to allow droplet size to equilibrate to within a desired size range; and continuing to polymerize the styrene monomer to polystyrene by suspension polymerization to produce gray EPS.
- a free radical initiator is used to catalyze the polymerization, and that the reaction mixture may also comprise, consist essentially of, and/or consist of sur
- the terms “comprising,” “including,” “containing,” “characterized by,” and grammatical equivalents thereof are inclusive or open-ended terms that do not exclude additional, unrecited elements or method acts, but also include the more restrictive terms “consisting of” and “consisting essentially of” and grammatical equivalents thereof.
- the term “may” with respect to a material, structure, feature or method act indicates that such is contemplated for use in implementation of an embodiment of the disclosure and such term is used in preference to the more restrictive term “is” so as to avoid any implication that other, compatible materials, structures, features and methods usable in combination therewith should or must be, excluded.
- the term “substantially” in reference to a given parameter, property, or condition means and includes to a degree that one of ordinary skill in the art would understand that the given parameter, property, or condition is met with a degree of variance, such as within acceptable manufacturing tolerances.
- the parameter, property, or condition may be at least 90.0% met, at least 95.0% met, at least 99.0% met, or even at least 99.9% met.
- the term “about” in reference to a given parameter is inclusive of the stated value and has the meaning dictated by the context (e.g., it includes the degree of error associated with measurement of the given parameter).
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Emergency Medicine (AREA)
- Inorganic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
TABLE 1 | ||||||
% styrene | % beads | % beads | % beads | |||
Experiment | at 3 hrs | < target | in target | >target | ||
1 | 6 | 26 | 45 | 29 | ||
2 | 24 | 8 | 26 | 66 | ||
3 | 48 | 28 | 42 | 30 | ||
4 | 41 | 30 | 41 | 29 | ||
-
- Examples 1 and 2 are comparative Examples using existing procedures. Example 1 showed a good percentage of beads in the target size, but Example 2 using the same conditions did not reproduce the results of Example 1.
- Example 3 and 4 are inventive Examples which show both good and consistent bead size distributions
Claims (15)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US15/787,083 US10544277B2 (en) | 2017-10-18 | 2017-10-18 | Process for making gray expanded polystyrene |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US15/787,083 US10544277B2 (en) | 2017-10-18 | 2017-10-18 | Process for making gray expanded polystyrene |
Publications (2)
Publication Number | Publication Date |
---|---|
US20190112447A1 US20190112447A1 (en) | 2019-04-18 |
US10544277B2 true US10544277B2 (en) | 2020-01-28 |
Family
ID=66095614
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/787,083 Active 2038-03-08 US10544277B2 (en) | 2017-10-18 | 2017-10-18 | Process for making gray expanded polystyrene |
Country Status (1)
Country | Link |
---|---|
US (1) | US10544277B2 (en) |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0668139A1 (en) | 1994-02-21 | 1995-08-23 | Sulzer Chemtech AG | Process for preparing expandable plastic granules |
EP0372343B1 (en) | 1988-11-25 | 2000-01-19 | The Dow Chemical Company | Polystyrene foam containing carbon black |
US6340713B1 (en) | 1997-05-14 | 2002-01-22 | Basf Aktiengesellschaft | Expandable styrene polymers containing graphite particles |
US6362242B1 (en) | 1997-09-29 | 2002-03-26 | Basf Aktiengesellschaft | Method for producing expandable styrene polymers |
US6414041B1 (en) * | 1998-11-16 | 2002-07-02 | Basf Aktiengesellschaft | Expandable styrene polymers containing graphite particles |
US6444714B1 (en) * | 1998-12-09 | 2002-09-03 | Basf Aktiengesellshaft | Method for producing expandable polystyrene particles |
EP1925418A1 (en) | 2006-11-23 | 2008-05-28 | Sulzer Chemtech AG | Method and device for manufacturing polymer particles |
US20090030096A1 (en) * | 2007-07-26 | 2009-01-29 | Korea Kumho Petrochemical Co., Ltd. | Method of producing expandable polystyrene beads which have excellent heat insulation properties |
US20130289146A1 (en) * | 2010-12-30 | 2013-10-31 | Cheil Industries Inc. | Foam Polystyrene-Based Bead and Method for Manufacturing the Same |
-
2017
- 2017-10-18 US US15/787,083 patent/US10544277B2/en active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0372343B1 (en) | 1988-11-25 | 2000-01-19 | The Dow Chemical Company | Polystyrene foam containing carbon black |
EP0668139A1 (en) | 1994-02-21 | 1995-08-23 | Sulzer Chemtech AG | Process for preparing expandable plastic granules |
US6340713B1 (en) | 1997-05-14 | 2002-01-22 | Basf Aktiengesellschaft | Expandable styrene polymers containing graphite particles |
US6362242B1 (en) | 1997-09-29 | 2002-03-26 | Basf Aktiengesellschaft | Method for producing expandable styrene polymers |
US6414041B1 (en) * | 1998-11-16 | 2002-07-02 | Basf Aktiengesellschaft | Expandable styrene polymers containing graphite particles |
US6444714B1 (en) * | 1998-12-09 | 2002-09-03 | Basf Aktiengesellshaft | Method for producing expandable polystyrene particles |
EP1925418A1 (en) | 2006-11-23 | 2008-05-28 | Sulzer Chemtech AG | Method and device for manufacturing polymer particles |
US20090030096A1 (en) * | 2007-07-26 | 2009-01-29 | Korea Kumho Petrochemical Co., Ltd. | Method of producing expandable polystyrene beads which have excellent heat insulation properties |
US20130289146A1 (en) * | 2010-12-30 | 2013-10-31 | Cheil Industries Inc. | Foam Polystyrene-Based Bead and Method for Manufacturing the Same |
Non-Patent Citations (3)
Title |
---|
Cottom, W. P., "Additives for Expanded Polystyrene Suspension Formulations", IP.com, IPCOM000244928D, Feb. 1, 2016. |
Lopes, Christina N., et al., "Effect of Initiator on the Incorporation of Graphite into Polymer Matrix During Suspension Polymerization", Macromol. Symp. 2005, 229, 72-80. |
Trommsdorff, U., et al., "Melt Impregnation Technology: Enhancement of the Thermal Resistance of EPS with Carbon Black", FOAMS 2015 Conference, Sep. 10-11, 2015, 7 pages. |
Also Published As
Publication number | Publication date |
---|---|
US20190112447A1 (en) | 2019-04-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7964652B2 (en) | Expandable polyethylene resin particle and method for production thereof | |
US5686518A (en) | Miniemulsion polymerization process using polymeric co-surfactant | |
US9394437B2 (en) | Polyethylene wax and brominated polymer in styrenic polymer | |
US6320006B1 (en) | Suspension polymerization process using suspending agent-containing slurry | |
AU2010329986B2 (en) | Process for the polymerization of styrene | |
JP5089920B2 (en) | Expandable polyethylene resin particles and method for producing the same | |
US10544277B2 (en) | Process for making gray expanded polystyrene | |
US10414895B2 (en) | Color development of carbon black in expanded polystyrene | |
US3072581A (en) | Foamable styrene polymer compositions and method for preparing same | |
US2857342A (en) | Steeping process for the preparation of foamable styrene polymer particles | |
JP2011052167A (en) | Styrene-modified polyethylene-based resin pre-expansion particle, expansion molded body and method for producing pre-expansion particle | |
WO2010110336A1 (en) | Method of reducing odor of composite resin particles, and composite resin particles | |
KR102538844B1 (en) | Method for preparing vinyl aromatic compound-vinylcyan compound copolymer and method for preparing thermoplastic resin composition comprising the copolymer | |
EP3087127A1 (en) | Use of sterically hindered styrene comonomer for improving the thermal stability of expanded vinyl aromatic polymer | |
JP3265246B2 (en) | Method for producing styrene resin particles | |
KR100536089B1 (en) | Method for Preparing Flame-Retardant Styrenic Resin with High Degree of Expansion Using a Small Amount of Blowing Agents | |
KR101713656B1 (en) | Method for producing expandable polystyrene large beads having excellent thermal insulation performance | |
MX2014006977A (en) | Method for producing expandable styrene polymers containing particulate additives. | |
US20020111451A1 (en) | Production of water-expandable styrene polymers | |
TR2023019487U5 (en) | Graphite Added Expandable Polystyrene Production Method | |
JPH0122842B2 (en) | ||
JP2007321020A (en) | Foamable polyethylene resin particle and its manufacturing method | |
JPS5962664A (en) | Resin composition for flame-retardant foam | |
JP2007308580A (en) | Expandable polyethylene resin particle and method for producing the same | |
KR20190086838A (en) | A method for manufacturing expandable polystyrene beads by subdividing seed particles |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
FEPP | Fee payment procedure |
Free format text: ENTITY STATUS SET TO UNDISCOUNTED (ORIGINAL EVENT CODE: BIG.); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION |
|
AS | Assignment |
Owner name: BAKER HUGHES, A GE COMPANY, LLC, TEXAS Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:HANNA, PAUL;HAZAIMEH, HAKIM;COTTOM, WILLIAM;AND OTHERS;SIGNING DATES FROM 20171024 TO 20171115;REEL/FRAME:045053/0812 |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: FINAL REJECTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NOTICE OF ALLOWANCE MAILED -- APPLICATION RECEIVED IN OFFICE OF PUBLICATIONS |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: PUBLICATIONS -- ISSUE FEE PAYMENT RECEIVED |
|
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
AS | Assignment |
Owner name: BAKER HUGHES HOLDINGS LLC, TEXAS Free format text: CHANGE OF NAME;ASSIGNOR:BAKER HUGHES A GE COMPANY, LLC;REEL/FRAME:052989/0256 Effective date: 20200415 |
|
AS | Assignment |
Owner name: NUCERA SOLUTIONS LLC, NEW YORK Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:BAKER HUGHES HOLDINGS LLC;REEL/FRAME:054166/0108 Effective date: 20200930 |
|
AS | Assignment |
Owner name: KEYBANK NATIONAL ASSOCIATION, AS ADMINISTRATIVE AGENT, OHIO Free format text: PATENT SECURITY AGREEMENT;ASSIGNOR:NUCERA SOLUTIONS LLC;REEL/FRAME:054571/0200 Effective date: 20200930 |
|
AS | Assignment |
Owner name: NUCERA SOLUTIONS LLC, OKLAHOMA Free format text: RELEASE OF SECURITY INTEREST IN PATENT COLLATERAL AT REEL/FRAME NO. 54571/0200;ASSIGNOR:KEYBANK NATIONAL ASSOCIATION, AS ADMINISTRATIVE AGENT;REEL/FRAME:061372/0144 Effective date: 20220901 |
|
MAFP | Maintenance fee payment |
Free format text: PAYMENT OF MAINTENANCE FEE, 4TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1551); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY Year of fee payment: 4 |
|
AS | Assignment |
Owner name: ANTARES CAPITAL LP, AS COLLATERAL AGENT, ILLINOIS Free format text: SECURITY INTEREST;ASSIGNORS:CHASE CORPORATION;NEPTCO INCORPORATED;NUCERA SOLUTIONS LLC;AND OTHERS;REEL/FRAME:065597/0771 Effective date: 20231115 |